High-performance oxygen evolution reaction (OER) catalyst is critical for improving the water splitting efficiency. In this work, an efficient self-supported OER catalyst was prepared by electrodeposition of nickel–iron layered double hydroxide nanosheets on titanium mesh substrate (NiFe-LDH/Ti-mesh). This self-supporting design exposes abundant active sites. At 100 mA cm−2, the NiFe-LDH/Ti-mesh shows a low overpotential of 310 mV in 1.0 M KOH. When assembled into an anion exchange membrane water electrolyzer, it can run stably over 200 h. In-situ Raman reveals that the NiFe-LDH/Ti-mesh surface was reconstructed into NiFeOOH active species. In-situ infrared shows that the introduction of Fe promotes the evolution of oxygen intermediates. Theoretical calculations reveal a weakened binding strength of *OH and accelerated formation of *O by the introduction of Fe. This study provides a facile approach for developing of self-supported high-performance OER electrocatalyst, and advances the understanding of the origin of NiFe-based catalysts as well.